US3875220A - Process for the preparation of methacrylic acid from methacrolein - Google Patents

Process for the preparation of methacrylic acid from methacrolein Download PDF

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US3875220A
US3875220A US40530973A US3875220A US 3875220 A US3875220 A US 3875220A US 40530973 A US40530973 A US 40530973A US 3875220 A US3875220 A US 3875220A
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catalyst
process
methacrolein
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methacrylic acid
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James F White
James R Rege
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Standard Oil Co
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/887Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8878Chromium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/28Molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/30Tungsten
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/31Chromium, molybdenum or tungsten combined with bismuth
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/887Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8877Vanadium, tantalum, niobium or polonium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/888Tungsten
    • B01J23/8885Tungsten containing also molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14Phosphorus; Compounds thereof
    • B01J27/186Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198Vanadium
    • B01J27/199Vanadium with chromium, molybdenum, tungsten or polonium
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts

Abstract

Catalysts containing phosphorus, vanadium and molybdenum have been found to be especially effective for the oxidation of methacrolein with molecular oxygen to obtain methacrylic acid. The catalysts may be optionally promoted with Bi, As, B, Ce, Cr, Ag, Fe, W, Pb, Mn, Tl, Te, Ni, Nb, B, Sn and/or Cu.

Description

United States Patent [1 1 White et al.

Apr. 1, 1975 PROCESS FOR THE PREPARATION OF METHACRYLIC ACID FROM METHACROLEIN [75] Inventors: James F. White, Shaker Heights;

James R. Rege, Kent, both of Ohio [73] Assignee: The Standard Oil Co., Cleveland,

Ohio

[22] Filed: Oct. 11, 1973 [21] Appl. No.: 405,309

[52] US. Cl 260/530 N, 252/432, 252/456, 252/464, 252/467, 252/469, 252/470,

[51] Int. Cl. C07c 57/04, C07c 51/30 [58] Field of Search 260/530 N, 533 N [56] References Cited UNITED STATES PATENTS 3,230,248 1/1966 Yanagita et al 260/530 N 3,435,069 3/1969 Bethell et al 260/530 N FOREIGN PATENTS OR APPLICATIONS 4l6,262 4/l966 Japan 260/530 N Primary Examiner Lorraine A. Weinberger Assistant ExaminerRichard D. Kelly Attorney, Agent, or FirmHerbert D. Knudsen [57] ABSTRACT 7 Claims, N0 Drawings PROCESS FOR THE PREPARATION OF METHACRYLIC ACID FROM METHACROLEIN BACKGROUND OF THE INVENTION A number of catalysts are known to be effective for the oxidation of acrolein to acrylic acid. Although the disclosure also states that the catalysts are useful for oxidizing methacrolein to methacrylic acid, the yields obtained using the catalysts for the preparation of methacrylic acid are low. The present invention is the result of a search specifically directed toward the oxidation of methacrolein.

SUMMARY OF THE INVENTION It has now been discovered in the process for the preparation of methacrylic acid from methacrolein by reacting methacrolein with molecular oxygen at a temperature of about 200 to about 500C. in the presence of a catalyst and optionally in the presence of steam. the improvement comprising using as the catalyst a catalyst having the formula wherein a is a positive number less than about 6;

b is about 0.1 to about l2; and

.\' is the number of oxygens required by the valence states of the other elements present said catalyst optionally containing one or more elements selected from the group consisting of bismuth, arsenic, boron. cerium, chromium, silver, iron. tungsten, nickel, niobium, lead. manganese, thallium, tellurium. boron, tin or copper. These catalysts given high per pass conversions to methacrylic acid and are very stable under the required operating conditions.

The central aspect of the invention is the catalyst used in a known process of preparing methacrylic acid from methacrolein. The catalyst may be any of the catalysts designated by the formula given above. The catalysts can be prepared by a number of different techniques described in the art, such as coprecipitation of soluble salts and calcination of the resulting product.

Preferred catalysts contain molybdenum in a valence state below +6. These catalysts are prepared by reducing and stabilizing the hexavalent molybdenum in the catalyst preparation. About 2 to about of the positive valence of hexavalent molybdenum is preferably reduced.

In the catalyst preparations, the various elements of the catalyst are combined. and the final product is calcined to obtain the catalyst. A number of methods of combining the elements of the catalyst and calcining the resultant product are known to those of skill in the art. In the broad concept of the invention, the particular method of preparing the catalyst is not critical.

There are, however, methods of preparing the catalysts that have been found to be preferred. One preferred preparation involves the refluxing of an aqueous mixture containing the appropriate amounts of phosphoric acid and molybdenum trioxide and adding vanadium trioxide. Another preferred preparation entails the reduction of hexavalent molybdenum with a reducing agent, and the use of this reduced molybdenum in the preparation of the catalyst. For example, molybdenum trioxide could be reacted with powdered molybdenum metal and the other elements to make up the desired catalysts and could be combined with the reduced molybdenum trioxide.

The calcination of the catalyst usually is accomplished by heating the dry catalytic components at a temperature of about 300 to about 700C. The particular calcination for the most desirable results varies as different catalysts are prepared. The best calcination conditions for catalysts of the invention are shown in the Specific Embodiments.

The catalysts of the invention have preferred limitations on their composition. Preferred are catalysts wherein a is about 0.5 to about 3, and catalysts wherein b is about 1 to about 6. Also preferred are catalysts which contain one or more of bismuth, arsenic, cerium, chromium, tin, tungsten, nickel or niobium. The catalysts of the invention can be simply and conveniently prepared from inexpensive metal oxides that are easy to handle.

The reaction of methacrolein with molecular oxygen to produce methacrylic acid is known even though the results obtained using this reaction have not been highly desirable. The present invention uses substantially the same conditions; therefore, these conditions need not be presented in detail.

The reactants of the reaction of the invention are methacrolein and molecular oxygen. Molecular oxygen is normally supplied to the reaction in the form of air, but oxygen gas could also be employed. About 0.5 to about 4 moles of oxygen are normally added per mole of methacrolein.

Optionally, added to the reactants is steam or an inert diluent. Preferred reactions are conducted in the presence of substantial quantities of steam in the range of about 2 to about 20 moles of steam per mole of methacrolein.

The reaction temperature may vary as different catalysts are employed. Normally, temperatures of about 200 to about 500C. are employed. with temperatures of less than about 400C. being preferred.

The reaction is conveniently conducted in either a fixed-bed or fluid-bed reactor. The contact time may be as low as a fraction of a second or as high as 20 seconds or more. The reaction may be conducted at atmospheric. superatmospheric or subatmospheric pressure, with absolute pressures of about 0.5 to about 4 atmospheres being preferred.

When used in the reactor, the catalyst may be in a supported or unsupported form. Suitable support materials include silica, alumina, boron phosphate, zirconia, titania and the like.

Using the catalysts of the invention in the preparation of methacrylic acid from methacrolein, good yields are obtained in a convenient reaction with low amounts of by-products.

SPECIFIC EMBODIMENTS EXAMPLES l-6 Preparation of methacrylic acid using catalysts containing PVMo Catalysts of the invention were prepared as follows:

EXAMPLE 1 A slurry consisting of 64.7 g. of molybdenum trioxide, 5.76 g. of phosphoric acid and 800 mls. of distilled water was refluxed for one hour. The color changed from white to greenish-yellow during this reflux. After reflux, 5.6 g. of vanadium trioxide was added and the slurry rapidly becomes dark blue. The slurry was boiled to dryness, dried in air at 1 l120C. for 12 hours.

EXAMPLE 2 This catalyst was prepared in the same manner as Example 1. except that 8.98 g. of vanadium trioxide was employed.

EXAMPLE 3 This catalyst was prepared in the same manner as Example 1 using 86.4 g. molybdenum trioxide. 7.6 g. of 85% phosphoric acid and 14.9 g. of vanadium trioxide.

EXAMPLES 46 The catalysts were prepared in the same manner as shown above using the appropriate ratio of ingredients.

The catalysts prepared above were ground and screened to recover these particles of to mesh size. A portion of these catalyst particles were placed in a 20 e.c. fixed-bed reactor constructed ofa 0.96 cm. inside diameter stainless steel tube heated in a split block furnace. The temperature inside of the reactor was monitored by a thermocouple.

The reactor was heated to reaction temperature under a flow of air and a feed of methacrolein/air/- steam of l/6.2/5.2 and was fed over the catalyst at an apparent contact time of four seconds. The weight of methacrolein fed/weight ofcatalyst/hour was 0.07. The reactor was run under the reaction conditions for 2 to 5 hours and then product was collected for 30 minutes and analyzed. The reaction conditions and results of the experiments are shown in Table 1. The following definitions are used measuring the carbon atoms in the feed and the products.

single pass yield (product recovered X l00)/(methacro1ein fed) "/1 conversion (methacrolein reacted X 100)/(methacrolein fed) 7( selectivity (methacrylic acid recovered 100)/(methaero1ein reacted) TABLE 1 The remaining products produced were carbon oxides with only small amounts of acrylic acid and acrolein being produced.

EXAMPLES 7-14 Element Compound Amount, g.

Ce eerie oxide 6.88 Sn stannic oxide 6.03 Bi bismuth trioxide 9.32 B boric acid 2.47 Cr chromic trioxide 3.04 Te tellurium dioxide 6.38 Ni nickel oxide 2.99 Nb niobium oxide 5.32

Following the addition of the optional element, the catalysts were boiled and dried according to Example 1.

The catalysts were ground, screened and tested as shown in the examples above. The results of using these catalysts in the oxidation of methacrolein are given in Table 11.

Preparation of Methacrylic Acid from Methacrolein Single Pass Yield. 7(

Temp.. F. Methacrylic Acetic Example Catalyst Bath Reactor Acid Acid Conv.. 71 Sel.. /2

l P V Mo O 343 356 57.0 5.4 80 72.5

2 P V Mo O, 343 361 48.2 6.0 77.4 62.3

6 P V Mo O 357 376 57.6 9.6 90.7 62.8

TABLE ll Conversion of Methacrolein to Methacrylic Acid Using u.x 1.a2 2.n 1a .r Temp. C. Single Pass Yield, /1 Example Catalyst. M= Bath Bed Methacrylic Acetic Conversion. "/1 Selectivity 7 Ce 343 361 49.7 7.3 84.5 67.1 8 Sn 316 329 50.8 4.9 74- 68.8 9 -Bi 343 357 46.9 4.6 67 10 B 343 364 49.5 7.5 84.9 58.6 11 Cr 357 371 44.4 7.2 88.1 50.4 12 Te 357 373 48.3 7.7 78 62 13 Ni 329 342 50.8 5.0 73.9 68.7 14 Nb 343 364 51.0 7.7 88.4 57.7

EXAMPLE Tungsten promoted catalyst 1n the same manner as described by the examples above, a catalyst of the formula W P V Mo O was prepared by dissolving l 1.5 g. of 85% phosphoric acid. 141.2 g. of ammonium heptamolybdate, 53.9 g. of ammonium paratungstate in 1,500 ml. of distilled water. The mixture was brought to a boil and 23.4 g. ofammonium vanadate was added. The catalyst preparation was completed as described above.

The catalyst was ground, screened and tested according to the examples above. The single pass yield to methacrylic acid was 51.2%, the single pass yield to acetic acid was 3.471, the conversion of the methacrolein was 82.8% and the selectivity to methacrylic acid was 62%.

We claim:

1. In the process for the preparation of methacrylic acid from methacrolein by reacting methacrolein with molecular oxygen at a temperature of about 200 to about 500C. in the presence of a catalyst and optionally in the presence of steam, the improvement comprising using a catalyst consisting essentially of phosphorous,

vanadium. molybdenum and oxygen, said catalyst having the formula wherein a is a positive number less than about 6;

b is about 0.1 to about 12;

,\' is the number of oxygens required by the valance states of the other elements present; and

wherein at least some of the molybdenum in the catalyst is maintained at a valence state below +6; said catalyst optionally containing one or more elements selected from the group consisting of bismuth, arsenic, boron, cerium. chromium, silver, iron, tungsten, nickel, niobium, lead, manganese, thallium, tellurium, tin or copper.

2. The process of claim 1 wherein the molybdenum in the catalyst is hexavalent molybdenum which has been reduced to lose about 2 to about 20% of its positive valance.

3. The process of claim 1 wherein the catalyst is prepared by refluxing an aqueous mixture containing at least molybdenum trioxide.

4. The process of claim 1 wherein a is about 0.5 to about 3.

5. The process of claim 1 wherein Z; is about 1 to about 6.

6. The process of claim 1 wherein the catalyst contains one or more of bismuth, arsenic, cerium, chromium, tin, tungsten, nickel or niobium.

7. The process of claim I conducted in the presence 0 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent NO. 3 875:22O Dated April 1,

t James R. Re e Q Inventor) James F Whl e and g It is certified that error appears in the aboveidentified patent and that said Letters Patent are hereby corrected as shown below:

Specific Embodiments, Table 1: Title In the title, F"

0 should be C Signed and Scaled this Nmth D3) of November 1976 [SEAL] AIIGSI.

UTH C. MfSON C. MARSHALL DANN Ancslmg Officer (ummissinm'r nj'Palents and Trademarks

Claims (7)

1. IN THE PROCESS FOR THE PREPARATION OF METHACRYLIC ACID FROM METHACROLEIN BY REACTING METHACROLEIN WITH MOLECULAR OXYGEN AT A TEMPERATURE OF ABOUT 200* TO ABOUT 500*C. IN THE PRESENCE OF A CATALYST AND OPTIONALLY IN THE PRESENCE OF STEAM, THE IMPROVEMENT COMPRISING USING A CATALYST CONSISTING ESSENTIALY OF PHOSPHOROUS, VANADIUM MOLYBDENUM AND OXYGEN, SAID CATALYST HAVING THE FORMULA
2. The process of claim 1 wherein the molybdenum in the catalyst is hexavalent molybdenum which has been reduced to lose about 2 to about 20% of its positive valance.
3. The process of claim 1 wherein the catalyst is prepared by refluxing an aqueous mixture containing at least molybdenum trioxide.
4. The process of claim 1 wherein a is about 0.5 to about 3.
5. The process of claim 1 wherein b is about 1 to about 6.
6. The process of claim 1 wherein the catalyst contains one or more of bismuth, arsenic, cerium, chromium, tin, tungsten, nickel or niobium.
7. The process of claim 1 conducted in the presence of steam.
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Cited By (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976688A (en) * 1973-11-26 1976-08-24 Nippon Zeon Co., Ltd. Process for preparing unsaturated carboxylic acids
FR2305424A1 (en) * 1975-03-27 1976-10-22 Standard Oil Co A process for preparing acrylic acid and methacrylic acid from the corresponding aldehydes
US3998877A (en) * 1974-04-02 1976-12-21 Asahi Glass Co., Ltd. Process for preparing methacrylic acid
US3998876A (en) * 1973-08-16 1976-12-21 Mitsubishi Rayon Co., Ltd. Catalytic process for preparation of unsaturated carboxylic acids
US4001316A (en) * 1973-06-15 1977-01-04 Nippon Kayaku Kabushiki Kaisha Method for manufacture of methacrylic acid
US4018709A (en) * 1975-03-17 1977-04-19 Petro-Tex Chemical Corporation Catalyst for preparing maleic anhydride from C4 hydrocarbons
DE2704991A1 (en) * 1976-02-09 1977-08-11 Toyo Soda Mfg Co Ltd A process for the production of methacrylic acid
US4042533A (en) * 1976-06-07 1977-08-16 The Standard Oil Company Producing unsaturated aliphatic acids
US4042623A (en) * 1974-09-24 1977-08-16 Nippon Kayaku Kabushiki Kaisha Method of manufacturing methacrylic acid and an oxidation catalyst
US4042625A (en) * 1974-07-03 1977-08-16 Mitsubishi Rayon Company, Ltd. Process and catalyst for preparing unsaturated carboxylic acid
US4051179A (en) * 1975-04-03 1977-09-27 Mitsubishi Rayon Co., Ltd. Catalytic process for the preparation of unsaturated carboxylic acids
US4056487A (en) * 1975-10-02 1977-11-01 Petro-Tex Chemical Corporation Vanadium phosphorus oxygen oxidation catalysts useful for preparing anhydrides from alkanes
US4070397A (en) * 1973-10-11 1978-01-24 Standard Oil Company Process for the preparation of methacrylic acid from the corresponding aldehyde
US4075123A (en) * 1976-10-19 1978-02-21 The Standard Oil Company Process for the preparation of unsaturated acids from unsaturated aldehydes
US4075244A (en) * 1973-11-22 1978-02-21 Nippon Zeon Co. Ltd. Process for preparing methacrylic acid
US4075124A (en) * 1976-10-19 1978-02-21 The Standard Oil Company Process for the preparation of unsaturated acids from unsaturated aldehydes
US4080312A (en) * 1973-07-19 1978-03-21 Phillips Petroleum Company Solid catalysts for oxidative dehydrogenation of alkenes or alkadienes to furan compounds
DE2739779A1 (en) * 1976-09-06 1978-03-30 Nippon Kayaku Kk Catalyst and its use in a method for producing methacrylic acid
US4092354A (en) * 1973-03-30 1978-05-30 Sumitomo Chemical Company, Limited Process for production of acrylic acid
US4101448A (en) * 1976-05-14 1978-07-18 The Standard Oil Company Catalyst compositions especially useful for preparation of unsaturated acids
US4105586A (en) * 1977-02-10 1978-08-08 Denka Chemical Corporation Oxidation catalysts and process for preparing anhydride from alkanes
US4113769A (en) * 1975-10-23 1978-09-12 Montedison S.P.A. Process for preparing unsaturated carboxylic acids by gas phase catalytic oxidation of the corresponding aldehydes
US4113770A (en) * 1974-03-14 1978-09-12 Nippon Zeon Co. Ltd. Process for preparing unsaturated carboxylic acids
US4138366A (en) * 1976-05-05 1979-02-06 The Standard Oil Company Process for producing unsaturated aliphatic acids and catalysts therefore
FR2398036A1 (en) * 1977-07-22 1979-02-16 Toyo Soda Mfg Co Ltd A process for preparing methacrylic acid by catalytic oxidation of methacrolein
US4157987A (en) * 1974-09-13 1979-06-12 Standard Oil Company Catalyst compositions especially useful for preparation of unsaturated acids
US4166190A (en) * 1973-10-11 1979-08-28 The Standard Oil Company Process for the preparation of methacrylic acid from methacrolein
US4167516A (en) * 1977-02-10 1979-09-11 Denka Chemical Corporation Preparation of dicarboxylic anhydrides
US4170570A (en) * 1978-01-03 1979-10-09 Standard Oil Company (Ohio) Process for preparing oxidation catalysts
US4177161A (en) * 1974-10-22 1979-12-04 Ube Industries, Ltd. Catalytic oxidative process for producing maleic anhydride
US4180678A (en) * 1973-12-29 1979-12-25 Nippon Shokubai Kagaku Kogyo Co. Ltd. Process for preparing methacrylic acid
US4184981A (en) * 1977-09-12 1980-01-22 Celanese Corporation Selective oxidation catalyst
US4202826A (en) * 1977-02-10 1980-05-13 Denka Chemical Corporation Process for preparing anhydride from alkanes
US4220802A (en) * 1974-07-26 1980-09-02 Nippon Zeon Co. Ltd. Process for the preparation of acrylic acid
US4225466A (en) * 1973-12-29 1980-09-30 Nippon Shokubai Kagaku Kogyo Co. Ltd. Catalytic oxide composition for preparing methacrylic acid
US4245118A (en) * 1978-01-17 1981-01-13 Nippon Zeon Co., Ltd. Oxidation of unsaturated aldehydes
US4246427A (en) * 1975-10-08 1981-01-20 Japan Synthetic Rubber Co., Ltd. Process for producing methacrylic acid
US4256914A (en) * 1978-08-25 1981-03-17 Ube Industries, Ltd. Catalytic oxidation of methacrolein
US4273676A (en) * 1977-10-31 1981-06-16 Nippon Kayaku Kabushiki Kaisha Process for producing methacrylic acid and a catalyst
US4339355A (en) * 1975-10-09 1982-07-13 Union Carbide Corporation Catalytic oxide of molybdenum, vanadium, niobium and optional 4th metal
US4341900A (en) * 1975-03-03 1982-07-27 Mitsubishi Rayon Company, Limited Catalytic process for the preparation of unsaturated carboxylic acid
US4358608A (en) * 1976-06-07 1982-11-09 The Standard Oil Company Process for producing unsaturated aliphatic acids
US4397771A (en) * 1975-01-13 1983-08-09 The Standard Oil Co. Oxidation catalysts
US4404397A (en) * 1980-03-24 1983-09-13 Air Products And Chemicals, Inc. High conversion of C3 and C4 olefins to corresponding unsaturated aldehydes and acids with stable molybdenum catalysts
US4530916A (en) * 1978-12-13 1985-07-23 Nippon Kayaku Kabushiki Kaisha Catalyst for use in a methacrylic acid process
US4596784A (en) * 1982-06-07 1986-06-24 Rohm And Haas Company Catalyst compositions and their use for the preparation of unsaturated carboxylic acids
US4917820A (en) * 1986-08-26 1990-04-17 Nippon Kayaku Kabushiki Kaisha Ethylene removal agent, postharvest preservation agent and deodorant
US4925980A (en) * 1978-06-21 1990-05-15 Nippon Kayaku Kabushiki Kaisha Process for producing methacrylic acid and a catalyst
EP0471853A1 (en) * 1990-03-13 1992-02-26 Nippon Shokubai Co., Ltd. Process for producing methacrylic acid
FR2667252A1 (en) * 1990-09-07 1992-04-03 Nippon Catalytic Chem Ind Catalyst and method of use.
US6281384B1 (en) 1998-06-26 2001-08-28 E. I. Du Pont Nemours And Company Vapor phase catalytic oxidation of propylene to acrylic acid
US6437193B1 (en) 1997-07-15 2002-08-20 E. I. Du Pont De Nemours And Company Vapor phase oxidation of propylene to acrolein

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1591307A (en) * 1976-11-11 1981-06-17 Ici Ltd Production of maleic anhydride and catalysts therefor
US4223161A (en) * 1977-03-31 1980-09-16 The Standard Oil Company (Ohio) Process for producing unsaturated aliphatic acids
US4212767A (en) * 1978-10-17 1980-07-15 Air Products And Chemicals, Inc. Method of preparing an oxidation catalyst containing a molybdate anion
US4280928A (en) * 1979-10-12 1981-07-28 Rohm And Haas Company Catalyst compositions and their use for the preparation of methacrolein
FR2495015B1 (en) * 1980-11-28 1985-07-05 Rhone Poulenc Chim Base Process for the preparation of catalysts based on molybdene oxides and / or tungstene and oxides of other metals
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US5378468A (en) * 1992-09-22 1995-01-03 The Mennen Company Composition containing body activated fragrance for contacting the skin and method of use
CN105753683A (en) * 2016-01-18 2016-07-13 吉林市吉化江城油脂化工有限责任公司 Method for preparing hydroxypivalic acid by catalytic oxidation of phosphotungstic acid

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3230248A (en) * 1961-07-18 1966-01-18 Rikagaku Kenkyusho Preparation of methyl or ethyl methacrylate
US3435069A (en) * 1960-04-14 1969-03-25 Distillers Co Yeast Ltd Oxidation of acrolein and methacrolein with a molybdenum polyvalent metaloxygen catalyst

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4744U (en) * 1971-05-21 1972-01-27
US3875220A (en) * 1973-10-11 1975-04-01 Standard Oil Co Ohio Process for the preparation of methacrylic acid from methacrolein

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3435069A (en) * 1960-04-14 1969-03-25 Distillers Co Yeast Ltd Oxidation of acrolein and methacrolein with a molybdenum polyvalent metaloxygen catalyst
US3230248A (en) * 1961-07-18 1966-01-18 Rikagaku Kenkyusho Preparation of methyl or ethyl methacrylate

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4092354A (en) * 1973-03-30 1978-05-30 Sumitomo Chemical Company, Limited Process for production of acrylic acid
US4001316A (en) * 1973-06-15 1977-01-04 Nippon Kayaku Kabushiki Kaisha Method for manufacture of methacrylic acid
US4080312A (en) * 1973-07-19 1978-03-21 Phillips Petroleum Company Solid catalysts for oxidative dehydrogenation of alkenes or alkadienes to furan compounds
US3998876A (en) * 1973-08-16 1976-12-21 Mitsubishi Rayon Co., Ltd. Catalytic process for preparation of unsaturated carboxylic acids
US4166190A (en) * 1973-10-11 1979-08-28 The Standard Oil Company Process for the preparation of methacrylic acid from methacrolein
US4070397A (en) * 1973-10-11 1978-01-24 Standard Oil Company Process for the preparation of methacrylic acid from the corresponding aldehyde
US4075244A (en) * 1973-11-22 1978-02-21 Nippon Zeon Co. Ltd. Process for preparing methacrylic acid
US3976688A (en) * 1973-11-26 1976-08-24 Nippon Zeon Co., Ltd. Process for preparing unsaturated carboxylic acids
US4180678A (en) * 1973-12-29 1979-12-25 Nippon Shokubai Kagaku Kogyo Co. Ltd. Process for preparing methacrylic acid
US4225466A (en) * 1973-12-29 1980-09-30 Nippon Shokubai Kagaku Kogyo Co. Ltd. Catalytic oxide composition for preparing methacrylic acid
US4113770A (en) * 1974-03-14 1978-09-12 Nippon Zeon Co. Ltd. Process for preparing unsaturated carboxylic acids
US4440948A (en) * 1974-04-02 1984-04-03 Asahi Glass Company, Ltd. Process for preparing methacrylic acid
US3998877A (en) * 1974-04-02 1976-12-21 Asahi Glass Co., Ltd. Process for preparing methacrylic acid
US4042625A (en) * 1974-07-03 1977-08-16 Mitsubishi Rayon Company, Ltd. Process and catalyst for preparing unsaturated carboxylic acid
US4220802A (en) * 1974-07-26 1980-09-02 Nippon Zeon Co. Ltd. Process for the preparation of acrylic acid
US4163862A (en) * 1974-09-13 1979-08-07 Standard Oil Company (Ohio) Preparation of unsaturated acids
US4157987A (en) * 1974-09-13 1979-06-12 Standard Oil Company Catalyst compositions especially useful for preparation of unsaturated acids
US4042623A (en) * 1974-09-24 1977-08-16 Nippon Kayaku Kabushiki Kaisha Method of manufacturing methacrylic acid and an oxidation catalyst
US4177161A (en) * 1974-10-22 1979-12-04 Ube Industries, Ltd. Catalytic oxidative process for producing maleic anhydride
US4397771A (en) * 1975-01-13 1983-08-09 The Standard Oil Co. Oxidation catalysts
US4341900A (en) * 1975-03-03 1982-07-27 Mitsubishi Rayon Company, Limited Catalytic process for the preparation of unsaturated carboxylic acid
US4018709A (en) * 1975-03-17 1977-04-19 Petro-Tex Chemical Corporation Catalyst for preparing maleic anhydride from C4 hydrocarbons
FR2305424A1 (en) * 1975-03-27 1976-10-22 Standard Oil Co A process for preparing acrylic acid and methacrylic acid from the corresponding aldehydes
US4051179A (en) * 1975-04-03 1977-09-27 Mitsubishi Rayon Co., Ltd. Catalytic process for the preparation of unsaturated carboxylic acids
US4056487A (en) * 1975-10-02 1977-11-01 Petro-Tex Chemical Corporation Vanadium phosphorus oxygen oxidation catalysts useful for preparing anhydrides from alkanes
US4246427A (en) * 1975-10-08 1981-01-20 Japan Synthetic Rubber Co., Ltd. Process for producing methacrylic acid
US4339355A (en) * 1975-10-09 1982-07-13 Union Carbide Corporation Catalytic oxide of molybdenum, vanadium, niobium and optional 4th metal
US4113769A (en) * 1975-10-23 1978-09-12 Montedison S.P.A. Process for preparing unsaturated carboxylic acids by gas phase catalytic oxidation of the corresponding aldehydes
DE2704991A1 (en) * 1976-02-09 1977-08-11 Toyo Soda Mfg Co Ltd A process for the production of methacrylic acid
US4174459A (en) * 1976-02-09 1979-11-13 Toyo Soda Manufacturing Co., Ltd. Process for producing methacrylic acid
US4138366A (en) * 1976-05-05 1979-02-06 The Standard Oil Company Process for producing unsaturated aliphatic acids and catalysts therefore
US4115441A (en) * 1976-05-14 1978-09-19 The Standard Oil Company Catalyst compositions especially useful for preparation of unsaturated acids
US4101448A (en) * 1976-05-14 1978-07-18 The Standard Oil Company Catalyst compositions especially useful for preparation of unsaturated acids
US4042533A (en) * 1976-06-07 1977-08-16 The Standard Oil Company Producing unsaturated aliphatic acids
US4358608A (en) * 1976-06-07 1982-11-09 The Standard Oil Company Process for producing unsaturated aliphatic acids
DE2739779A1 (en) * 1976-09-06 1978-03-30 Nippon Kayaku Kk Catalyst and its use in a method for producing methacrylic acid
US4075124A (en) * 1976-10-19 1978-02-21 The Standard Oil Company Process for the preparation of unsaturated acids from unsaturated aldehydes
US4075123A (en) * 1976-10-19 1978-02-21 The Standard Oil Company Process for the preparation of unsaturated acids from unsaturated aldehydes
US4202826A (en) * 1977-02-10 1980-05-13 Denka Chemical Corporation Process for preparing anhydride from alkanes
US4105586A (en) * 1977-02-10 1978-08-08 Denka Chemical Corporation Oxidation catalysts and process for preparing anhydride from alkanes
US4167516A (en) * 1977-02-10 1979-09-11 Denka Chemical Corporation Preparation of dicarboxylic anhydrides
FR2398036A1 (en) * 1977-07-22 1979-02-16 Toyo Soda Mfg Co Ltd A process for preparing methacrylic acid by catalytic oxidation of methacrolein
US4178464A (en) * 1977-07-22 1979-12-11 Toyo Soda Manufacturing Co., Ltd. Process for producing methacrylic acid
US4184981A (en) * 1977-09-12 1980-01-22 Celanese Corporation Selective oxidation catalyst
US4273676A (en) * 1977-10-31 1981-06-16 Nippon Kayaku Kabushiki Kaisha Process for producing methacrylic acid and a catalyst
US4170570A (en) * 1978-01-03 1979-10-09 Standard Oil Company (Ohio) Process for preparing oxidation catalysts
US4245118A (en) * 1978-01-17 1981-01-13 Nippon Zeon Co., Ltd. Oxidation of unsaturated aldehydes
US4925980A (en) * 1978-06-21 1990-05-15 Nippon Kayaku Kabushiki Kaisha Process for producing methacrylic acid and a catalyst
US4256914A (en) * 1978-08-25 1981-03-17 Ube Industries, Ltd. Catalytic oxidation of methacrolein
US4530916A (en) * 1978-12-13 1985-07-23 Nippon Kayaku Kabushiki Kaisha Catalyst for use in a methacrylic acid process
US4404397A (en) * 1980-03-24 1983-09-13 Air Products And Chemicals, Inc. High conversion of C3 and C4 olefins to corresponding unsaturated aldehydes and acids with stable molybdenum catalysts
US4596784A (en) * 1982-06-07 1986-06-24 Rohm And Haas Company Catalyst compositions and their use for the preparation of unsaturated carboxylic acids
US4917820A (en) * 1986-08-26 1990-04-17 Nippon Kayaku Kabushiki Kaisha Ethylene removal agent, postharvest preservation agent and deodorant
EP0471853A1 (en) * 1990-03-13 1992-02-26 Nippon Shokubai Co., Ltd. Process for producing methacrylic acid
EP0471853A4 (en) * 1990-03-13 1992-09-09 Nippon Shokubai Co., Ltd. Process for producing methacrylic acid
US5239115A (en) * 1990-03-13 1993-08-24 Nippon Shokubai Co., Ltd. Method for producing methacrylic acid
FR2667252A1 (en) * 1990-09-07 1992-04-03 Nippon Catalytic Chem Ind Catalyst and method of use.
US6437193B1 (en) 1997-07-15 2002-08-20 E. I. Du Pont De Nemours And Company Vapor phase oxidation of propylene to acrolein
US6281384B1 (en) 1998-06-26 2001-08-28 E. I. Du Pont Nemours And Company Vapor phase catalytic oxidation of propylene to acrylic acid

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